Metal Complexes of Polydentate Beta-Ketoiminates

ABSTRACT

A plurality of metal-containing complexes of a polydentate beta-ketoiminate, one embodiment of which is represented by the structure are shown: 
     
       
         
         
             
             
         
       
         
         
           
             wherein M is a metal such as calcium, strontium, barium, scandium, yttrium, lanthanum, titanium, zirconium, vanadium, tungsten, manganese, cobalt, iron, nickel, ruthenium, zinc, copper, palladium, platinum, iridium, rhenium, osmium; wherein R 1  is selected from the group consisting of alkyl, fluoroalkyl, cycloaliphatic, and aryl, having from 1 to 10 carbon atoms; R 2  can be from the group consisting of hydrogen, alkyl, alkoxy, cycloaliphatic, and aryl; R 3  is linear or branched selected from the group consisting of alkylene, fluoroalkyl, cycloaliphatic, and aryl; R 4  is an alkylene bridge; R 5-6  are individually linear or branched selected from the group consisting of alkyl, fluoroalkyl, cycloaliphatic, aryl, and they can be connected to form a ring containing carbon, oxygen, or nitrogen atoms; n is an integer equal to the valence of the metal M.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of Provisional U.S. PatentApplication No. 60/794,820 filed Apr. 25, 2006.

BACKGROUND OF THE INVENTION

The semiconductor fabrication industry continues to metal sourcecontaining precursors for chemical vapor deposition processes includingatomic layer deposition for fabricating conformal metal containing filmson substrates such as silicon, metal nitride, metal oxide and othermetal-containing layers using these metal-containing precursors.

BRIEF SUMMARY OF THE INVENTION

This invention is directed to metal containing polydentateβ-ketoiminates and solutions wherein the polydentate β-ketoiminatesincorporate nitrogen or oxygen functionality in the imino group. Thepolydentate β-ketoiminates are selected from the group represented bythe structures:

wherein M is a metal having a valence of from 2 to 5. Examples of metalsinclude calcium, strontium, barium, scandium, yttrium, lanthanum,titanium, zirconium, vanadium, tungsten, manganese, cobalt, iron,nickel, ruthenium, zinc, copper, palladium, platinum, iridium, rhenium,and osmium. A variety of organo groups may be employed as for examplewherein R¹ is selected from the group consisting of alkyl, fluoroalkyl,cycloaliphatic, and aryl, having from 1 to 10 carbon atoms, preferably agroup containing 1 to 6 carbon atoms; R² is selected from the groupconsisting of hydrogen, alkyl, alkoxy, cycloaliphatic, and aryl; R³ isselected from the group consisting of alkyl, fluoroalkyl,cycloaliphatic, and aryl; R⁴ is an alkylene bridge, preferably a groupcontaining 2 or 3 carbon atoms, thus making a five- or six-memberedcoordinating ring to the metal center; R⁵⁻⁶ are individually selectedfrom the group consisting of alkyl, fluoroalkyl, cycloaliphatic, aryl,and they can be connected to form a ring containing carbon, oxygen, ornitrogen atoms. The subscript n is an integer and equals the valence ofthe metal M.

wherein M is a metal ion selected from Group 4, 5 metals includingtitanium, zirconium, and hafnium; wherein R¹ is selected from the groupconsisting of alkyl, fluoroalkyl, cycloaliphatic, and aryl, preferably agroup containing 1 to 6 carbon atoms; R² is selected from the groupconsisting of hydrogen, alkyl, alkoxy, cycloaliphatic, and aryl; R³ isselected from the group consisting of alkyl, fluoroalkyl,cycloaliphatic, and aryl; R⁴ is an alkylene bridge, preferably a groupcontaining 2 or 3 carbon atoms, thus making a five- or six-memberedcoordinating ring to the metal center; R⁵⁻⁶ are individually selectedfrom the group consisting of alkyl, fluoroalkyl, cycloaliphatic, aryl,and they can be connected to form a ring containing carbon, oxygen, ornitrogen atoms; R⁷ is selected from the group consisting of alkyl,fluoroalkyl, cycloaliphatic, and aryl; wherein m and n are at least 1and the sum of m+n is equal to the valence of the metal.

wherein M is an alkaline earth metal with specific examples includingcalcium, strontium, barium; R¹ is selected from the group consisting ofalkyl, fluoroalkyl, cycloaliphatic, and aryl, preferably a groupcontaining 1 to 6 carbon atoms; R² is selected from the group consistingof hydrogen, alkyl, alkoxy, cycloaliphatic, and aryl; R³ is selectedfrom the group consisting of alkyl, fluoroalkyl, cycloaliphatic, andaryl; R⁴⁻⁵ are each a 2 carbon atom alkylene bridge, thus making afive-membered coordinating ring to the metal center; R⁶⁻⁷ areindividually selected from the group consisting of alkyl, fluoroalkyl,cycloaliphatic, aryl, or they can be connected to form a ring containingcarbon, oxygen, or nitrogen atoms; and X is either an oxygen, or anitrogen substituted with a hydrogen, an alkyl or an aryl group.

Several advantages can be achieved through these metal-containingpolydentate β-ketoiminates as precursors for chemical vapor depositionor atomic layer deposition, and these include:

-   -   an ability to form reactive complexes in good yield;    -   an ability to form monomeric complexes, particularly strontium        and barium complexes, coordinated with one kind of ligand, thus        allowing one to achieve a high vapor pressure;    -   an ability to produce highly conformal metal thin films suited        for use in a wide variety of electrical applications;    -   an ability to form highly conformal metal oxide thin films        suited for use in microelectronic devices;    -   an ability to enhance the surface reaction between the        metal-containing polydentate β-ketoiminates and the surface of a        substrate due to the high chemical reactivity of the complexes;        and,    -   an ability to tune the physical property of these        metal-containing polydentate β-ketoiminates via a change in the        R¹⁻⁷ groups.

DETAILED DESCRIPTION OF THE DRAWINGS

FIG. 1 is a drawing representative of the crystal structure ofbis(2,2-dimethyl-5-(dimethylaminoethyl-imino)-3-hexanonato-N,O,N′)strontium.

FIG. 2 is a TGA diagram ofbis(2,2-dimethyl-5-(dimethylaminoethyl-imino)-3-hexanonato-N,O,N′)strontium,indicating the complex is volatile but decomposes at higher temperature.

FIG. 3 is a drawing representing the crystal structure oftris(2,2-dimethyl-5-(dimethylaminoethyl-imino)-3-hexanonato)ytterium.

FIG. 4 is a drawing representative of the crystal structure ofbis(2,2-dimethyl-5-(dimethylaminoethyl-imino)-3-hexanonato)cobalt.

FIG. 5 is a drawing representative of the crystal structure ofbis(2,2-dimethyl-5-(dimethylaminoethyl-imino)-3-hexanonato)nickel.

FIG. 6 is a drawing representative of the crystal structure oftris(tert-butoxy()(4-(dimethylaminoethyl-imino)-2-hexanonato)zirconium(IV).

FIG. 7 is a TGA diagram oftris(tert-butoxy)(4-(dimethylaminoethyl-imino)-2-hexanonato)zirconium(IV),indicating the complex is volatile with less than 2% residue.

FIG. 8 is a drawing representing the crystal structure ofbis(2,2-dimethyl-5-(2-(2-(dimethylamino-ethyl)(methylamino))ethyl-imino)-3-hexanonato)barium.

FIG. 9 is a TGA/DSC diagram of the TGA/DSC ofbis(2,2-dimethyl-5-(dimethylaminoethyl-imino)-3-hexanonato-N,O,N′)strontiumbefore (dashed line) and after (solid line) dissolving in NMP,suggesting thatbis(2,2-dimethyl-5-(dimethylaminoethyl-imino)-3-hexanonato-N,O,N′)strontiumand NMP are compatible.

DETAILED DESCRIPTION OF THE INVENTION

This invention is related to metal-containing polydentate β-ketoiminateprecursors and their solutions which are useful for fabricatingconformal metal containing films on substrates such as silicon, metalnitride, metal oxide and other metal layers via deposition processes,e.g., CVD and ALD. Such conformal metal containing films haveapplications ranging from computer chips, optical device, magneticinformation storage, to metallic catalyst coated on a supportingmaterial. In contrast to prior polydentate β-ketoiminate precursors, thepolydentate β-ketoiminate ligands incorporate at least one amino organoimino functionality which is in contrast to the literatures reportedalkoxy group as the donating ligand.

Oxidizing agents for vapor deposition process include oxygen, hydrogenperoxide and ozone and reducing agents for deposition processes includehydrogen, hydrazine, monoalkylhydrazine, dialkylhydrazine, and ammonia.

One type of structure in the metal precursor is illustrated in structure1A below where the metal M has a valence of 2 having the formula:

wherein M is selected from group 2, 8, 9, 10 metal atoms. In thisprecursor it is preferred that R¹ is a C₁₋₁₀ alkyl group, preferably at-butyl or t-pentyl group when the metal is strontium and barium andC₁₋₅ when cobalt or nickel, R² and R³ are methyl groups R⁵ and R⁶ areindividually lower C₁₋₃, preferably methyl groups and R⁴ is a C₂₋₃alkylene bridge, preferably an ethylene group. Preferred metals arecalcium, strontium, barium, iron, cobalt, and nickel.

Another type of structure within the first class of metal complexescontaining polydentate β-ketoiminate ligands is illustrated in structure2A below where the metal M has a valence of 3 having the formula:

wherein M is selected from group 3 metal atoms. In this precursor it ispreferred that R¹ is a C₄₋₆ alkyl group, preferably a t-butyl andt-pentyl group, R² and R³ are methyl groups, R⁵ and R⁶ are individuallylower C₁₋₃ alkyl, preferably methyl groups, and R⁴ is a C₂₋₃ alkylenebridge, preferably an ethylene group. Preferred metals are scandium,yttrium, and lanthanum.

The second class of metal-containing precursors are comprised ofpolydentate β-ketoiminate ligands as shown in formula B:

wherein M is a Group 4 or 5 metal such as titanium, zirconium, orhafnium. As shown the complex consists of at least one alkoxy ligand anda polydentate β-ketoiminato ligand having at least one amino organoimino. The preferred R¹⁻⁶ groups are the same as in formula A. Thepreferred R⁷ group is a linear or branched alkyl, e.g., iso-propyl,butyl, sec-butyl, and tert-butyl, m and n are at least 1 and the sum ofm+n is equal to the valence of the metal

The last class of metal-containing polydentate β-ketoiminate precursorsare shown in formula C:

wherein M is an alkaline earth metal wherein R¹ is selected from thegroup consisting of alkyl, fluoroalkyl, cycloaliphatic, and aryl, havingfrom 1 to 10 carbon atoms; R²⁻³ are individually selected from the groupconsisting of hydrogen, alkyl, alkoxy, cycloaliphatic, and aryl; R⁴⁻⁵are individually C₂₋₃ alkylene bridges, preferably ethylene groups, R⁶⁻⁷are individually selected from the group consisting of alkyl,fluoroalkyl, cycloaliphatic, aryl, and heterocyclic containing a oxygen,or nitrogen atom; X is either an oxygen, or nitrogen substituted with ahydrogen, an alkyl or an aryl group.

The polydentate β-ketoiminate ligands can be prepared by well knownprocedure such as the Claisen condensation of a bulky ketone and anethyl ester in presence of a strong base such as sodium amide orhydride, followed by another known procedure such as Schiff basecondensation reaction with alkylaminoalkylamine.

The ligands can be purified via vacuum distillation for a liquid orcrystallization for solid.

As a preferred method for the formation of high yield polydentateligands, it is preferred to choose a bulky R¹ group, e.g., C₄₋₁₀ alkylgroups without hydrogen attached to the carbon connected to the ketonefunctionality, most preferred R¹ group is tert-butyl or tert-pentyl. TheR¹ group prevents side reactions occurring in the following Schiffcondensation and later protecting the metal centers from inter-molecularinteraction. There is a competing issue and that is that the R¹⁻⁷ groupsin the polydentate ligands should be as small as possible in order todecrease the molecular weight of the resulting metal-containingcomplexes and allow the achievement of complexes having a high vaporpressure. The preferred R⁴⁻⁵ groups contain 2 to 3 carbon atoms in orderto make the resulting complexes more stable via forming a five- orsix-membered coordinating ring to the metal center.

The metal-containing complexes can then be prepared via the reaction ofthe resulting tridentate ligands with pure metal, metal amide, metalhydride, and metal alkoxide. The metal-containing complexes can also beprepared via reacting the polydentate ligand with alkyl lithium orpotassium hydride to provide the lithium or potassium salt of theligand, then followed by reaction with metal halide, MX₂ (X═Cl, Br, I).The group 4 and 5 mixed ligand complexes can be made via changing theratio of metal alkoxide to the polydentate ligands.

These metal-containing complexes with polydentate β-ketoiminate ligandscan be employed as potential precursors to make thin metal or metaloxide films via either the chemical vapor deposition (CVD) or atomiclayer deposition (ALD) method at temperatures less than 500° C. The CVDprocess can be carried out with or without reducing or oxidizing agentswhereas an ALD process usually involves the employment of anotherreactant such as a reducing agent or oxidizing agent.

For multi-component metal oxide, these complexes can be premixed if theyhave the same polydentate β-ketoiminate ligands. These metal-containingcomplexes with polydentate β-ketoiminate ligands can be delivered invapor phase into a CVD or ALD reactor via well-known bubbling or vapordraw techniques. A direct liquid delivery method can also be employed bydissolving the complexes in a suitable solvent or a solvent mixture toprepare a solution with a molar concentration from 0.001 to 2 Mdepending the solvent or mixed-solvents employed.

The solvent employed in solubilizing the precursor for use in adeposition process may comprise any compatible solvent or their mixtureincluding aliphatic hydrocarbons, aromatic hydrocarbons, ethers, esters,nitrites, and alcohols. The solvent component of the solution preferablycomprises a solvent selected from the group consisting of glyme solventshaving from 1 to 20 ethoxy —(C₂H₄O)— repeat units; C₂-C₁₂ alkanols,organic ethers selected from the group consisting of dialkyl etherscomprising C₁-C₆ alkyl moieties, C₄-C₈ cyclic ethers; C₁₂-C₆₀ crownO₄-O₂₀ ethers wherein the prefixed C_(i) range is the number i of carbonatoms in the ether compound and the suffixed O_(i) range is the number iof oxygen atoms in the ether compound; C₆-C₁₂ aliphatic hydrocarbons;C₆-C₁₈ aromatic hydrocarbons; organic esters; organic amines, polyaminesand organic amides.

Another class of solvents that offers advantages is the organic amideclass of the form RCONR′R″ wherein R and R′ are alkyl having from 1-10carbon atoms and they can be connected to form a cyclic group (CH₂)_(n),wherein n is from 4-6, preferably 5, and R″ is selected from alkylhaving from 1 to 4 carbon atoms and cycloalkyl. N-methyl andN-cyclohexyl 2-pyrrolidinones are examples.

The following example illustrates the preparation of themetal-containing complexes with polydentate β-ketoiminate ligands aswell as their use as precursors in metal-containing film depositionprocesses.

EXAMPLE 1 Synthesis of2,2-dimethyl-5-(dimethylaminoethyl-imino)-3-hexanone

In a 500 mL Schlenk flask, 29.3 g (206 mmol) of2,2-dimethyl-3,5-hexanedione and 24 g (170 mmol) anhydrous Na₂SO₄ wereloaded with 200 mL THF. To the flask, 20.08 g (228 mmol)3-(dimethylamino)ethylamine in 20 mL of THF was dropwise added. Thereaction mixture was stirred for three days. Upon completion, the GC/MSanalysis of the reaction mixture indicated the reaction was completewith trace amount 3-(dimethylamino)ethylamine. All volatiles wereremoved by distillation at temperature below 130° C. Subsequently theresulting slight yellow solution was vacuum distilled via a short-pathapparatus. Crystallization from hexanes provided about 36 g of a whitecrystal with a yield of 82%. GC analysis of the crystals dissolved inhexane only shows one observable GC peak besides the hexane. The solidcrystals were found to have a melting point of 28-30° C.

¹H NMR (500 MHz, C₆D₆): δ=11.30 (s, 1H, C(O)CHC(NH)), 5.15 (s, 1H,C(O)CHC(NH)), 2.80 (m, 2H, HNCH₂CH₂N(CH₃)₂), 2.05 (t, 2H,HNCH₂CH₂N(CH₃)₂), 1.95 (s, 6H, N(CH₃)₂), 1.50 (s, 3H, C(NH)CH₃), 1.35(s, 9H, C(CH₃)₃).

EXAMPLE 2 Synthesis of2,2-dimethyl-5-(diethylaminoethyl-imino)-3-hexanone

In a procedure analogously to2,2-dimethyl-5-(dimethylaminoethyl-imino)-3-hexanone, starting with2,2-dimethylhexa-3,5-dione (5.07 g, 36 mmol), Na₂SO₄ (3.5 g, 24.66mmol), and 3-(diethylamino)ethylamine (5.25 g, 45 mmol). Anorange/yellow liquid was obtained via a short-path vacuum distillationapparatus after removal of all volatiles. The yield is 78%.

¹H NMR (500 MHz, C₆D₆): δ=11.27 (s, 1H, C(O)CHC(NH)), 5.16 (s, 1H,C(O)CHC(NH)), 2.82 (m, 2H, HNCH₂CH₂N(CH₂CH₃)₂), 2.26 (q, 4H,N(CH₂CH₃)₂), 2.20 (t, 2H, HNCH₂CH₂N(CH₂CH₃)₂), 1.55 (s, 3H), 1.25 (s,9H, C(CH₃)₃), 0.86 (t, 6H, N(CH₂CH₃)₂).

EXAMPLE 3 Synthesis of2,2-dimethyl-5-(dimethylaminopropyl-imino)-3-hexanone

In a procedure analogously to2,2-dimethyl-5-(dimethylaminoethyl-imino)-3-hexanone, starting with2,2-dimethylhexa-3,5-dione (19.27 g, 136 mmol), Na₂SO₄ (13 g, 92 mmol),and 3-(dimethylamino)propylamine (15.72 g, 154 mmol). A yellow liquidwas obtained via a short-path vacuum distillation apparatus afterremoval of all volatiles. The yield is 89%.

¹H NMR (500 MHz, C₆D₆): δ=11.30 (s, 1H, C(O)CHC(NH)), 5.17 (s, 1H,C(O)CHC(NH)), 2.84 (q, 2H, HNCH₂CH₂N(CH₃)₂), 2.05 (t, 2H,HNCH₂CH₂CH₂N(CH₃)₂), 1.94 (s, 6H, N(CH₃)₂), 1.54 (s, 3H, C(NH)CH₃), 1.32(m, 2H, HNCH₂CH₂CH₂N(CH₃)₂), 1.27 (s, 9H, C(CH₃)₃).

EXAMPLE 4 Synthesis of2,2-dimethyl-5-(diethylaminopropyl-imino)-3-hexanone

In a procedure analogously to2,2-dimethyl-5-(dimethylaminoethyl-imino)-3-hexanone, starting withstarting with 2,2-dimethylhexa-3,5-dione (3.50 g, 25 mmol), Na₂SO₄ (4.81g, 34 mmol), and 3-(dimethylamino)propylamine (3.57 g, 27 mmol). Theresulting light yellow/green liquid was vacuum distilled via ashort-path apparatus to provide a yield of 67%.

¹H NMR (500 MHz, C₆D₆): δ=11.41 (s, 1H, C(O)CHC(NH)), 5.17 (s, 1H,C(O)CHC(NH)), 2.84 (q, 2H, HNCH₂CH₂N(CH₃)₂), 2.28 (q, 4H, N(CH₂CH₃)₂),2.19 (t, 2H, HNCH₂CH₂CH₂N(CH₂CH₃)₂), 1.53 (s, 3H, C(NH)CH₃), 1.33 (m,2H, HNCH₂CH₂CH₂N(CH₂CH₃)₂), 1.28 (s, 9H, C(CH₃)₃), 0.86 (t, 6H,N(CH₂CH₃)₂).

EXAMPLE 5 Synthesis of 4-(dimethylaminoethyl-imino)-2-pentanone

In a procedure analogously to2,2-dimethyl-5-(dimethylaminoethyl-imino)-3-hexanone, starting withstarting with 2,4-pentadione (8.00 g, 80.7 mmol), Na₂SO₄ (14 g, 98.64mmol), and 3-(dimethylamino)ethylamine (7.83 g, 88.8 mmol). A greenliquid was obtained via vacuum distillation at an oil bath of 95-105° C.under 150 mTorr. The yield was 83%. GC analysis indicated one peak.

¹H NMR (500 MHz, C₆D₆): δ=11.11(br, s, 1H, C(O)CHC(NH)), 4.88 (s, 1H,C(O)CHC(NH)), 2.78 (m, 2H, HNCH₂CH₂N(CH₃)₂), 2.01 (t, 3H,HNCH₂CH₂N(CH₃)₂), 2.00 (s, 3H, C(O)CH₃), 1.93 (s, 6H, N(CH₃)₂), 1.47 (s,3H, C(NH)CH₃).

EXAMPLE 6 Synthesis ofbis(2,2-dimethyl-5-(dimethylaminoethyl-imino)-3-hexanonato-N,O,N′)strontium

40.0 g (0.066 mol) of Sr(N(SiMe₃)₂)₂.2THF was loaded in a 500 mL Schlenkflask with 100 ml THF. To this flask was dropwise added 29.0 g (0.14mol) wax-like 2,2-dimethyl-5-(dimethylaminoethyl-imino)-3-hexanone in100 mL of THF. The resulting light yellow clear solution was stirred atroom temperature over night. All volatiles were then removed undervacuum to give a yellow solid which was dissolved in 100 mL of hothexanes. GC/MS analysis of the trapped volatile liquid indicated itcontains THF and by-product hexamethylsilylamine. GC/MS of the yellowsolid dissolving in THF revealed there is only2,2-dimethyl-5-(dimethylaminoethyl-imino)-3-hexanone besides THF,suggesting the solid contains the tridentate β-ketoiminate ligand. Thehexanes solution was then concentrated to about 30 mL to precipitatewhite crystals on the bottom. The flask was kept at −20° C. to affordmore colorless crystals. 26.1 g of the crystals was collected and driedunder vacuum. The yield is 77% on the basis of strontium.

Elemental analysis: calcd for C₂₄H₄₆N₄O₂Sr: C, 56.49; N, 10.98; H, 9.09.Found: C, 56.34; N, 11.32; H, 8.91. ¹H NMR (500 MHz, C₆D₆): δ=5.16 (s,2H), 2.97 (t, 4H), 2.26 (b, 4H), 1.89 (s, 12H), 1.77 (s, 6H), 1.37 (s,18H).

A colorless crystal ofbis(2,2-dimethyl-5-((dimethylaminoethylene)imino)-3-hexanonato)strontiumwas structurally characterized by X-ray single crystal analysis (seeFIG. 1). The structure below shows strontium is coordinated with two2,2-dimethyl-5-(dimethylamino)ethylene)imino)-3-hexanonato ligands in adistorted octahedral environment. The Sr—N distances range from 2.614 to2.690 Å and the average Sr—O is 2.353 Å. FIG. 2 exhibits a TGA diagramof bis(2,2-dimethyl-5-(dimethylaminoethyl-imino)-3-hexanonato-N,O,N′)strontium, indicating the complex is volatile but decomposes at highertemperature.

EXAMPLE 7 Synthesis ofbis(2,2-dimethyl-5-(diethylaminoethyl-imino)-3-hexanonato-N,O,N′)strontium

In a procedure analogously to example 6, starting withSr(N(SiMe₃)₂)₂.2THF (2.66 g, 0.005 mol) and2,2-dimethyl-5-(diethylaminoethyl-imino)-3-hexanone (2.0 g, 0.008 mol).1.91 g of the crystals was collected and dried under vacuum afterremoval of all volatiles and work-up. The yield is 84% on the basis ofstrontium.

Elemental analysis: calcd for C₂₈H₅₄N₄O₂Sr: C, 59.38; N, 9.89; H, 9.61.Found: C, 58.99; N, 9.90; H, 9.51. ¹H NMR (500 MHz, C₆D₆): δ=5.14 (s,2H), 2.11 (t, 4H), 2.67 (b, 4H), 2.54 (b, 8), 1.76 (s, 6H), 1.36 (s,18H), 0.74 (t, 12H).

A colorless crystal ofbis(2,2-dimethyl-5-(diethylaminoethyl-imino)-3-hexanonato)strontium wasstructurally characterized by X-ray single crystal analysis. Thestructure below shows strontium is coordinated with two2,2-dimethyl-5-(diethylaminoethyl-imino)-3-hexanonato ligands in adistorted octahedral environment. The Sr—N distances range from 2.604 to2.677 Å and the average Sr—O is 2.374 Å.

EXAMPLE 8 Synthesis oftris(2,2-dimethyl-5-(dimethylaminoethyl-imino)-3-hexanonato)yttrium

In a procedure analogously to example 6, starting with Y(N(SiMe₃)₂)₃(2.00 g, 3.9 mmol)) and2,2-dimethyl-5-(dimethylaminoethyl-imino)-3-hexanone (2.41 g, 11.35mmol). 1.57 g of white solid was collected and the yield is 57% on thebasis of yttrium.

Elemental analysis: calcd for C₃₆H₆₉N₆O₃Y: C, 59.81; N, 9.63; H, 11.63.Found: C, 59.81; N, 9.37; H, 11.83. ¹H NMR (500 MHz, C₆D₆): d=5.14 (s,3H), 3.47 (t, 6H), 2.49 (t, 6H), 2.22 (s, 18H), 1.81 (s, 9H), 1.27 (s,27H).

A colorless crystal oftris(2,2-dimethyl-5-(dimethylaminoethyl-imino)-3-hexanonato)yttrium wasstructurally characterized by X-ray single crystal analysis (see FIG.3), revealing that the yttrium atom is coordinated with three2,2-dimethyl-5-(dimethylaminoethyl-imino)-3-hexanonato ligands.

EXAMPLE 9 Synthesis ofbis(2,2-dimethyl-5-(dimethylaminoethyl-imino)-3-hexanonato)cobalt

Procedures (a) and (b) are shown for producing this compound. (a) 2 g(0.015 mol) of anhydrous CoCl₂ was loaded in a 500 mL Schlenk flask with30 ml THF. To this flask was added(2,2-dimethyl-5-(dimethylaminoethyl-imino)-3-hexanonato)Li prepared insitu by the reaction of2,2-dimethyl-5-(dimethylaminoethyl-imino)-3-hexanone (6.4 g, 0.03 mol)with a 2.5 M LiBu^(n) hexane solution (12 mL, 0.03 mol) in 40 mL ofhexanes at −78° and stirred at room temperature for 30 min. The mixturewas stirred at room temperature over night. After the reaction wascomplete, all volatiles were then removed under vacuum to give rise to adark brown solid. Extraction and filtration produced a dark brownsolution and brown solid. The brown was LiCl contaminated with traceamount of Co compounds. The brown solution was then dried at 50° C. toyield a dark brown solid. Sublimation of the dark brown solid at 105° C.and 50 Torr provide greenish brown microcrystals. The yield is 50% onthe basis of cobalt.

Elemental Analysis for CoC₂₄H₄₆N₄O₂: C, 59.86; N, 11.63; H, 9.63. Found:C, 59.73; N, 11.62; H, 9.77. ¹H NMR (500 MHz, C₆D₆): δ=119.04, 25.38,11.86, 3.42, 1.36, 0.43, −16.00, −97.00.

Procedure (b) A single crystal ofbis(2,2-dimethyl-5-(dimethylaminoethyl-imino)-3-hexanonato) cobalt wascharacterized by X-ray single crystal analysis (see FIG. 4), exhibitingthat the cobalt atom is coordinated with two2,2-dimethyl-5-(diethylaminoethyl-imino)-3-hexanonato ligands in adistorted octahedral environment.

(b). NaH (0.34 g, 14 mmol) was slowly added to a solution of2,2-dimethyl-5-(diethylaminoethyl-imino)-3-hexanone (2.07 g, 12 mmol) in70 mL of THF. After bubbling ceased, CoCl₂ (1.07 g, 8 mmol) was added toreaction flask. 2.25 g of brown crystals were collected after workup andthe yield was 69%.

EXAMPLE 10 Synthesis ofbis(2,2-dimethyl-5-(dimethylaminopropyl-imino)-3-hexanonato)cobalt

In a procedure similar to example 9, starting with2,2-dimethyl-5-(dimethylaminopropylene-imino)-3-hexanone (1.50 g, 0.007mol) and (0.22 g, 0.009 mol) NaH (0.22 g, 0.009 mol), CoCl₂ (0.38 g,0.003 mol) was added. Following workup, the orange crystals wereobtained by sublimation of the resulting brown solid. The yield is 82%.

Elemental Analysis for CoC₂₆H₅₀N₄O₂: C, 61.27; N, 10.99; H, 9.89. Found:C, 61.42; N, 11.19; H, 9.43. ¹H NMR (500 MHz, C₆D₆): δ=14.40, 8.83,1.42, −1.45, −5.54, −21.49, −31.91.

A single crystal ofbis(2,2-dimethyl-5-(dimethylaminopropyl-imino)-3-hexanonato) cobalt wascharacterized by X-ray single crystal analysis, exhibiting that thecobalt atom is coordinated with two2,2-dimethyl-5-(dimethylaminopropyl-imino)-3-hexanonato ligands in anoctahedral environment.

EXAMPLE 11 Synthesis ofbis(4-(dimethylaminoethyl-imino)-2-hexenonato)cobalt

In a procedure similar to example 9, starting with (2.07 g, 0.012 mol)4-(dimethylaminoethyl-imino)-2-hexenone (2.07 g, 0.012 mol) and (0.34 g,0.14 mol) NaH, followed by addition of CoCl₂ (1.07 g, 0.008 mol) wasadded. Crystals were grown from a hexane solution and the yield is 69%.

Elemental Analysis for CoC₁₈H₃₄N₄O₂: C, 54.40; N, 14.83; H, 8.62. Found:C, 54.72; N, 14.04; H, 10.10. ¹H NMR (500 MHz, C₆D₆): δ=25.47, 17.44,8.69, 1.35, −9.47, −12.00, −21.40, −116.00, 120.04.

EXAMPLE 12 Synthesis ofbis(2,2-dimethyl-5-(dimethylaminoethyl-imino)-3-hexanonato)nickel

In a procedure similar to example 9, starting with (3.48 g, 0.016 mol)2,2-dimethyl-5-(dimethylaminoethyl-imino)-3-hexanone (3.48 g, 0.016 mol)and 2.5M butyl lithium (6.5 mL, 0.016 mol), followed by addition ofNiCl₂ (1.02 g, 0.008 mol) was added. Upon sublimation the bright greensolid was obtained with a yield of 66%.

Elemental Analysis for NiC₂₄H₄₆N₄O₂: C, 59.89; N, 11.63; H, 9.63. Found:C, 60.80; N, 11.62; H, 8.80.

A single crystal ofbis(2,2-dimethyl-5-(dimethylaminoethyl-imino)-3-hexanonato) nickel wascharacterized by X-ray single crystal analysis (see FIG. 5), exhibitingthat the nickel atom is coordinated with two2,2-dimethyl-5-(dimethylaminoethyl-imino)-3-hexanonato ligands in anoctahedral environment.

EXAMPLE 13 Synthesis ofbis(2,2-dimethyl-5-(dimethylaminopropyl-imino)-3-hexanonato)nickel

In a procedure similar to example 9, starting with2,2-dimethyl-5-(dimethylaminopropyl-imino)-3-hexanone (3.66 g, 0.016mol) and 2.5M butyl lithium (6.3 mL, 0.015 mol) followed by addition ofNiCl₂ (1.01 g, 0.008 mol) was added. Green crystals were harvested fromhexane solution.

Elemental Analysis for NiC₂₆H₅₀N₄O₂: C, 61.30; N, 11.52; H, 9.89. Found:C, 61.52; N, 11.06; H, 9.34. ¹H NMR (500 MHz, C₆D₆): δ=60.00, 36.56,3.57, 1.47, −2.84, 14.70, 16.10, −76.00.

A single crystal ofbis(2,2-dimethyl-5-(dimethylaminopropyl-imino)-3-hexanonato) nickel wascharacterized by X-ray single crystal analysis, exhibiting that thenickel atom is coordinated with two(2,2-dimethyl-5-(dimethylaminopropyl-imino)-3-hexanonato) ligands in anoctahedral environment.

EXAMPLE 14 Synthesis ofbis(4-(dimethylaminoethyl-imino)-2-hexanonato)nickel

In a procedure similar to Example 9, starting with4-(dimethylaminoethyl-imino)-2-hexanone (2.15 g, 0.013 mol) and NaH(0.36 g, 0.015 mol), and NiCl₂ (0.74 g, 0.006 mol) was added. Theproduct was sublimed and crystallized from hexane. Yield is 74%.

Elemental Analysis for NiC₁₈H₃₄N₄O₂: C, 54.43; N, 14.10; H, 8.63. Found:C, 54.21; N, 14.04; H, 10.10.

EXAMPLE 15 Synthesis oftris(isopropoxy)(2,2-dimethyl-5-(dimethylaminoethyl-imino)-3-hexanonato)titanium(IV)

Ti (OCH(CH3)2)4(2.00 g, 0.007 mol), (1.45 g, 0.007 mol)2,2-dimethyl-5-(dimethylaminoethyl-imino)-3-hexanone(1.45 g, 0.007 mol),and 15 mL hexane were loaded into a 100 mL Schlenk flask. The mixturewas stirred at 40° C. for 16 hours. Under vacuum all volatiles wereremoved, and the yellow powdery solid was washed with hexane and dried.Sublimation provides the light green crystals with a yield of 90%.

¹H NMR (500 MHz, C₆D₆): δ=5.18 (s, 1H), s, 1H), 5.00 (b, 3H), 2.96 (s,2H), 2.48 (s, 6H), 2.28 (t, 2H), 1.53 (s, 3H), 1.35 (s, 9H), 1.30 (s,18H).

EXAMPLE 16 Synthesis oftris(isopropoxy)(4-(dimethylaminoethyl-imino)-2-hexenonato)titanium

In a procedure similar to Example 15, stirring (2.08 g, 0.007 mol) Ti(OCH(CH₃)₂)₄ and (1.19 g, 0.007 mol)5-(dimethylaminoethyl-imino)-3-hexanonato. Sublimation of the stickyyellow solid produced light green crystals, yielding 74%.

Elemental Analysis for C₁₈H₃₈N₂O₄Ti: C, 54.82; N, 9.71; H, 7.10. Found:C, 52.50; N, 9.50; H, 7.39. ¹H NMR (500 MHz, C₆D₆): δ=4.92 (b, 3H) 4.83(s, 1H), 2.96 (s, 2H), 2.47(s, 6H), 2.27 (t, 2H), 1.95 (s, 3H), 1.45 (s,6H), 1.30 (s, 18H).

A single crystal oftris(isopropoxy)(4-(dimethylaminoethyl-imino)-3-hexanonato)titanium wascharacterized by X-ray single crystal analysis, exhibiting that theTitanium atom was coordinated with three isopropoxy groups and one5-(dimethylaminoethyl-imino)-3-hexanonato ligand.

EXAMPLE 17 Synthesis oftris(tert-butoxy)(4-(dimethylaminoethyl-imino)-2-hexanonato)hafnium(IV)

In a procedure similar to Example 15, starting with Hf(OC(CH₃)₃)₄ (2.73g, 0.006 mol) and 5-(dimethylaminoethyl-imino)-3-hexanone (1.01 g, 0.005mol). Volatiles were examined via GC/MS, and 2-methyl-2-propanol wasobserved. The white solid was collected with a yield of 95%.Crystallization from pentane/hexane solution provides colorlessblock-like crystals.

¹H NMR (500 MHz, C₆D₆): δ=4.81 (s, 1H), 2.89 (t, 2H), 2.44 (s, 8H), 1.55(s, 9H), 1.42 (s, 3H), 1.36 (s, 18H)

EXAMPLE 18 Synthesis oftris(tert-butoxy)(2,2-dimethyl-5-(dimethylaminoethyl-imino)-3-hexanonato)zirconium(IV)

In a procedure similar to Example 15, starting with Zr(OC(CH₃)₃)₄ (1.81g, 0.005 mol) and 2,2-dimethyl-5-(dimethylaminoethyl-imino)-3-hexanone((1.05 g, 0.005 mol). Workup provided a light yellow solid with a yieldof 95%.

¹H NMR (500 MHz, C₆D₆): δ=4.86 (s, 1H, BuCOCHCN), 2.91 (b, t, 2H,NCH₂CH₂NMe₂), 2.39 (b, s, 6H, CH₂N(CH₃)₂), 2.39 (b, t, 2H, NCH₂CH₂NMe₂),1.55 (s, 9H, (CH₃)₃CCO), 1.49 (s, 3H, COCHCN(CH₃)), 1.31 (s, 27H,(OC(CH₃)₃)

A colorless crystal oftris(tert-butoxy)(2,2-dimethyl-5-(dimethylaminoethyl-imino)-3-hexanonato)zirconium(IV)was characterized by X-ray single crystal analysis, exhibiting that thezirconium atom was coordinated with three tert-butoxy groups and onesubstituted 2,2-dimethyl-5-(dimethylaminoethyl-imino)-3-hexanonatoligand.

EXAMPLE 19 Synthesis oftris(tert-butoxy)(4-(dimethylaminoethyl-imino)-2-hexanonato)zirconium(IV)

In a procedure similar to Example 15, stirring (2.2 g, 0.006 mol)Zr(OC(CH₃)₃)₄ (2.2 g, 0.006 mol) and5-(dimethylaminoethyl-imino)-3-hexanone (1.0 g, 0.006 mol) in THFproduced a light yellow solid with a yield of 82% upon workup.

¹H NMR (500 MHz, C₆D₆): δ=4.86 (s, 1H, CH₃COChCN), 2.90 (s, 2H,NCH₂CH₂NMe₂), 2.36 (b, s, 6H, CH₂N(CH₃)₂), 2.36 (b, t, 2H, NCH₂CH₂NMe₂),1.89 (s, 3H, CH₃COCHCN), 1.51 (s, 9H, CH₃(CH₃)₂)COCH), 1.41 (s, 3H,CH₃COCHCNCH₃), 1.35 (s, 18H, (CH₃)₂(CH₃)COCH)

A colorless crystal of tris(tert-butoxy()(4-(dimethylaminoethyl-imino)-2-hexanonato)zirconium(IV) wascharacterized by X-ray single crystal analysis (see FIG. 6), exhibitingthat the zirconium atom was coordinated with three tert-butoxy groupsand one substituted 4-(dimethylaminoethyl-imino)-2-hexanonato ligand.FIG. 7 reveals that a TGA diagram oftris(tert-butoxy)(4-(dimethylaminoethyl-imino)-2-hexanonato)zirconium(IV),indicating the complex is volatile with less than 2% residue.

EXAMPLE 20 Synthesis ofbis(2,2-dimethyl-5-(dimethylaminoethyl-imino)-3-hexanonato)barium

In a procedure analogously to example 6, starting withBa(N(SiMe₃)₂)₂.2THF and2,2-dimethyl-5-(diethylaminoethyl-imino)-3-hexanone. A very viscousorange oil was obtained upon removal of all volatiles. NMR indicatesthere are some unreacted2,2-dimethyl-5-(diethylaminoethyl-imino)-3-hexanone. The free ligand wasremoved via a short-path distillation to provide an orange solid.

¹H NMR (500 MHz, C₆D₆): δ=5.11 (br, s), 3.10 (br, s), 2.21 (br, s), 1.95(br, s), 1.80 (s, 6H), 1.38 (s).

EXAMPLE 21 Synthesis oftetrakis(ethoxy)(4-(dimethylaminoethyl-imino)-2-hexanonato)tantalum(V)

2,2-dimethyl-(5-(dimethylamino)propyl-imino)-3-hexenone (0.64 g, 3.8mmol) was slowly added a flask Loaded with Ta₂(OEt)₁₀ (1.50 g, 1.85mmol) to added. The flask was heated to 80° C. for 3 hours and then theby-product ethanol was removed under vacuum to yield 1.6 g of clearorange liquid. The yield is 1.6 g, 98%.

¹H NMR (500 MHz, C₆D₆): δ=4.79 (s, 1H), 4.76 (q, 2H), 4.71 (q, 2H), 4.31(q, 2H), 4.28 (q, 2H), 3.74 (t, 2H), 2.60 (t, 2H), 2.13 (s, 6H), 1.85(s, 3H), 1.70 (s, 3H), 1.40 (t, 3H), 1.38 (t, 3H), 1.20 (t, 6H).

EXAMPLE 22 Synthesis of2,2-dimethyl-5-(2-(2-(dimethylamino)ethoxy)ethyl-imino)-3-hexanone

In a 100 mL round bottom flask equipped with a magnetic stirrer, 8 g2,2-dimethylhexane-3,5-dione was combined with 1.1 equivalents of2-(2-(dimethylamino)ethoxy)ethylamine, anhydrous sodium sulfate andanhydrous diethyl ether and stirred over three days under nitrogen. Theether was removed on a rotary evaporator and the residue was vacuumdistilled through a Vigreux column to yield 9.7 g of product.

¹H NMR: (300 MHz, THF_(d8)): δ=11.05 (s, 1H), 5.06 (s, 1H), 3.51 (t,2H), 3.50 (t, 2H), 3.37 (q, 2H), 2.42 (t, 2H), 2.17 (s, 6H), 1.92 (s,3H), 1.05 (s, 9H).

EXAMPLE 23 Synthesis ofbis(2,2-dimethyl-5-(2-(2-(dimethylamino)ethoxy)ethyl-imino)-3-hexanonato)barium

In a 100 mL Schlenk flask with magnetic stirrer, in a glove box, 1.25 gsublimed barium metal was combined with 3.15 g2,2-dimethyl-5-(2-(2-(dimethylamino)ethoxy)ethyl-imino)-3-hexanone and30 mL anhydrous THF. The flask was placed on a Schlenk line and fittedwith a cold finger condenser. Anhydrous ammonia was allowed to condenseinto the flask and refluxed with the cold finger condenser for 4 hours.The flask and condenser were allowed to warm up to room temperature overnight and the ammonia was allowed to escape through a gas bubbler. Thecloudy amber solution was filtered through celite and the product wascrystallized from hot hexanes as white crystals.

¹H NMR: (300 MHz, THF_(d8)): δ=4.64 (s, 1H), 3.94 (t, 2H), 3.71 (t, 2H),3.51 (t, 2H), 2.49 (t, 2H), 2.18 (s, 6H), 1.78 (s, 3H), 1.10 (s, 9H).

EXAMPLE 24 Synthesis of2,2-dimethyl-5-(2-(2-(dimethylamino-ethyl)(methylamino))ethyl-imino)-3-hexanone

in a 100 mL round bottom flask equipped with a magnetic stirrer, 1.9 g2,2-dimethylhexane-3,5-dione was combined with 1.1 equivalents of2-(2-(dimethylamino-ethyl)(methylamino))ethylamine, anhydrous sodiumsulfate and anhydrous diethyl ether and stirred over night undernitrogen. The ether was removed on a rotary evaporator and the residuewas vacuum distilled through a Vigreux column to yield 2.7 g of product.

¹H NMR: (300 MHz, THFd₈): δ=10.99 (s, 1H), 5.06 (s, 1H), 3.28 (Q, 2H),2.53 (t, 2H), 2.48 (t, 2H), 2.37 (t, 2H), 2.25 (s, 3H), 2.15 (s, 6H),1.92 (s, 3H), 1.06 (s, 9H).

EXAMPLE 25 Synthesis ofbis(2,2-dimethyl-5-(2-(2-(dimethylamino-ethyl)(methylamino))ethyl-imino)-3-hexanonato)barium

In a 50 mL Schlenk flask with magnetic stirrer, in a glove box, 1.05 gsublimed barium metal was combined with 2.72 g2,2-dimethyl-5-(2-(2-(dimethylamino-ethyl)(methylamino))ethyl-imino)-3-hexanoneand 20 mL anhydrous THF. The flask was placed on a Schlenk line andfitted with a cold finger condenser. Anhydrous ammonia was allowed tocondense into the flask and refluxed with the cold finger condenser for4 hours. The flask and condenser were allowed to warm up to roomtemperature over night and the ammonia was allowed to escape through agas bubbler. The cloudy grayish suspension was concentrated, suspendedin hot hexanes and filtered through celite. The product wasrecrystallized from hot hexanes several times to give 0.4 g product ascolorless crystals.

Elemental analysis: calcd for C₃₀H₆₀BaN₆O₂: C, 53.45; N, 12.47; H, 8.97.Found: C, 53.33; N, 12.71; H, 9.44. ¹H NMR (500 MHz, C₆D₆): δ=5.07(s,1H), 3.28 (br, s, 2H), 2.49 (very br, 6H), 2.23 (s, 6H), 2.22 (sh, 3H),1.84 (s, 3H), 1.40 (s, 9H).

A single crystal ofbis(2,2-dimethyl-5-(2-(2-(dimethylamino-ethyl)(methylamino))ethyl-imino)-3-hexanonato)bariumwas characterized by X-ray single crystal analysis, exhibiting that thebarium atom is coordinated with two2,2-dimethyl-5-(2-(2-(dimethylamino-ethyl)(methylamino))ethyl-imino)-3-hexanonatoligands in tetradentate fashion.

EXAMPLE 26 Preparation of 1M solution ofbis(2,2-dimethyl-5-(dimethylaminoethyl-imino)-3-hexanonato-N,O,N′)strontiumin N-methyl-2-pyrrolidinone

To 1 ml vial containing 0.25 g ofbis(2,2-dimethyl-5-(dimethylaminoethyl-imino)-3-hexanonato-N,O,N′)strontium,0.49 ml of N-methyl-2-pyrrolidinone (NMP) was added to result in a paleyellow clear solution. The solution was kept at room temperature overnight and then dried under vacuum to give a pale yellow solid. FIG. 9shows the TGA/DSC ofbis(2,2-dimethyl-5-(dimethylaminoethyl-imino)-3-hexanonato-N,O,N′)strontiumbefore and after dissolving in NMP, suggesting thatbis(2,2-dimethyl-5-(dimethylaminoethyl-imino)-3-hexanonato-N,O,N′)strontiumand NMP are compatible and the resulting solution can be used in CVD orALD processes.

EXAMPLE 27 Preparation of 1.0M solution ofbis(2,2-dimethyl-5-(dimethylaminoethyl-imino)-3-hexanonato-N,O,N′)strontiumin N-cyclohexyl-2-pyrrolidinone

0.19 mL N-cyclohexyl-2-pyrrolidinone was added to a 2 mL vial containingbis(2,2-dimethyl-5-(dimethylaminoethyl-imino)-3-hexanonato-N,O,N′)strontium(0.10 g, 0.20 mmol) to result in a light green clear solution. TGA ofthe solution indicates the mixture is volatile.

EXAMPLE 28 Preparation of 0.9M solution oftris(isopropoxy)(4-(dimethylaminoethyl-imino)-2-hexenonato)titanium inN-methyl-2-pyrrolidinone

0.27 mL N-methyl-2-pyrrolidinone was added to a 2 mL vial containingtris(isopropoxy)(4-(dimethylaminoethyl-imino)-2-hexenonato)titanium (0.1g, 0.25 mmol) to result in a bright orange solution. TGA of the solutionindicates the mixture is volatile.

EXAMPLE 29 Preparation of 0.75M solution of tris(tert-butoxy()(4-(dimethylaminoethyl-imino)-2-hexanonato)zirconium(IV) inN-methyl-2-pyrrolidinone

0.28 mL N-methyl-2-pyrrolidinone was added to a 2 mL vial containingtris(tert-butoxy()(4-(dimethylaminoethyl-imino)-2-hexanonato)zirconium(IV) (0.10 g, 0.21mmol) to result in a greenish yellow solution. TGA of the solutionindicates the mixture is volatile.

1. A metal containing complex represented by the structures selectedfrom the group consisting of:

wherein M is a metal group having a valence of from 2 to 5 wherein R¹ isselected from the group consisting of alkyl, fluoroalkyl,cycloaliphatic, and aryl, having from 1 to 10 carbon atoms; R² isselected from the group consisting of hydrogen, alkyl, alkoxy,cycloaliphatic, and aryl; R³ is selected from the group consisting ofalkyl, fluoroalkyl, cycloaliphatic, and aryl; R⁴ is an alkylene bridge;R⁵⁻⁶ are individually selected from the group consisting of alkyl,fluoroalkyl, cycloaliphatic, aryl, and heterocyclic containing eitheroxygen, or nitrogen atoms; n is an integer equal to the valence of themetal M;

wherein M is a metal ion selected from Group 4 and 5 metals; wherein R¹is selected from the group consisting of alkyl, fluoroalkyl,cycloaliphatic, and aryl, having from 1 to 10 carbon atoms; R² isselected from the group consisting of hydrogen, alkyl, alkoxy,cycloaliphatic, and aryl; R³ is selected from the group consisting ofalkyl, fluoroalkyl, cycloaliphatic, and aryl; R⁴ is an alkylene bridge;R⁵⁻⁶ are individually selected from the group consisting of alkyl,fluoroalkyl, cycloaliphatic, aryl, or heterocyclic containing an oxygen,or nitrogen atom; R⁷ is selected from the group consisting of alkyl,fluoroalkyl, cycloaliphatic, and aryl; and wherein m and n are at least1 and the sum of m plus n is equal to the valence of the metal M; and,

wherein M is an alkaline earth metal wherein R¹ is selected from thegroup consisting of alkyl, fluoroalkyl, cycloaliphatic, and aryl, havingfrom 1 to 10 carbon atoms; R²⁻³ are individually selected from the groupconsisting of hydrogen, alkyl, alkoxy, cycloaliphatic, and aryl; R⁴⁻⁵are individually C₂₋₃ alkylene bridges; R⁶⁻⁷ are individually selectedfrom the group consisting of alkyl, fluoroalkyl, cycloaliphatic, aryl,and heterocyclic containing a oxygen, or nitrogen atom; X is either anoxygen, or nitrogen substituted with a hydrogen, an alkyl or an arylgroup.
 2. The metal containing complex of claim 1 structure A wherein Mis selected from the group consisting of calcium, strontium, barium,scandium, yttrium, lanthanum, titanium, zirconium, vanadium, tungsten,manganese, cobalt, iron, nickel, ruthenium, zinc, copper, palladium,platinum, iridium, rhenium, and osmium.
 3. The metal containing complexof claim 2 wherein M is selected from the group consisting of Ca, Sr,and Ba.
 4. The metal containing complex of claim 3 wherein R¹ isselected from the group from t-butyl and t-pentyl, R² and R³ areindividually selected from the group consisting of methyl and ethyl, R⁴is a C₂ alkylene bridge, and R⁵ and R⁶ are individually selected fromthe group consisting of methyl and ethyl.
 5. The metal containingcomplex of claim 3 wherein M is strontium, R¹ is t-butyl, R² and R³ aremethyl, R⁴ is a C₂ alkylene bridge and R⁵ and R⁶ are methyl.
 6. Themetal containing complex of claim 3 wherein M is strontium, R¹ ist-butyl, R² and R³ are methyl, R⁴ is a C₂ alkylene bridge and R⁵ and R⁶are ethyl.
 7. The metal containing complex of claim 3 wherein M isselected from the group consisting of Fe, Co, and Ni.
 8. The metalcontaining complex of claim 7 wherein R¹ is selected from the groupconsisting of C₁₋₆ alkyl, R² and R³ are individually selected from thegroup consisting of methyl and ethyl, R⁴ is a C₂₋₃ alkylene bridge, andR⁵ and R⁶ are individually selected from the group consisting of methyland ethyl.
 9. The metal containing complex of claim 7 wherein M iscobalt, R¹ is methyl, R² and R³ are methyl, R⁴ is a C₂ alkylene bridgeand R⁵ and R⁶ are methyl.
 10. The metal containing complex of claim 7wherein M is cobalt, R¹ is t-butyl, R² and R³ are methyl, R⁴ is a C₂alkylene bridge and R⁵ and R⁶ are methyl.
 11. The metal containingcomplex of claim 7 wherein M is cobalt, R¹ is methyl, R² and R³ aremethyl, R⁴ is a C₃ alkylene bridge and R⁵ and R⁶ are methyl.
 12. Themetal containing complex of claim 7 wherein M is cobalt, R¹ is t-butyl,R² and R³ are methyl, R⁴ is a C₃ alkylene bridge and R⁵ and R⁶ aremethyl.
 13. The metal containing complex of claim 7 wherein M is nickel,R¹ is methyl, R² and R³ are methyl, R⁴ is a C₂ alkylene bridge and R⁵and R⁶ are methyl.
 14. The metal containing complex of claim 7 wherein Mis nickel, R¹ is t-butyl, R² and R³ are methyl, R⁴ is a C₂ alkylenebridge and R⁵ and R⁶ are methyl.
 15. The metal containing complex ofclaim 7 wherein M is nickel, R¹ is methyl, R² and R³ are methyl, R⁴ is aC₃ alkylene bridge and R⁵ and R⁶ are methyl.
 16. The metal containingcomplex of claim 7 wherein M is nickel, R¹ is t-butyl, R² and R³ aremethyl, R⁴ is a C₃ alkylene bridge and R⁵ and R⁶ are methyl.
 17. Themetal containing complex of claim 2 wherein M is selected from the groupconsisting of Y, La, Pr, Ce, Sm, Er, Yb, and Lu.
 18. The metalcontaining complex of claim 17 wherein R¹ is selected from the groupconsisting of C₁₋₅ alkyl, R² and R³ are individually selected from thegroup consisting of methyl and ethyl, R⁴ is a C₂₋₃ alkylene bridge, andR⁵ and R⁶ are individually selected from the group consisting of methyland ethyl.
 19. The metal containing complex of claim 17 wherein M is Y,R¹ is t-butyl, R² and R³ are methyl, R⁴ is a C₂ alkylene bridge and R⁵and R⁶ are methyl.
 20. The metal containing complex of claim 17 whereinM is Y, R¹ is t-butyl, R² and R³ are methyl, R⁴ is a C₃ alkylene bridgeand R⁵ and R⁶ are methyl.
 21. The metal containing complex of claim 17wherein M is La, R¹ is t-butyl, R² and R³ are methyl, R⁴ is a C₂alkylene bridge and R⁵ and R⁶ are methyl.
 22. The metal containingcomplex of claim 15 wherein M is La, R¹ is t-butyl, R² and R³ aremethyl, R⁴ is a C₃ alkylene bridge and R⁵ and R⁶ are methyl.
 23. Themetal containing complex of claim 1 represented by the structure B:wherein M is selected from the group consisting of titanium, zirconium,hafnium, vanadium, niobium, and tantalum.
 24. The metal containingcomplex of claim 23 wherein R¹ is selected from the group consisting ofC₁₋₅ alkyl, R² and R³ are individually selected from the groupconsisting of methyl and ethyl, R⁴ is a C₂₋₃ alkylene bridge, R⁵ and R⁶are individually selected from the group consisting of methyl and ethyl,and R⁷ is selected the group consisting of methyl, ethyl, propyl,iso-propyl, n-butyl, sec-butyl, and tert-butyl.
 25. The metal containingcomplex of claim 23 wherein M is Ti, R¹ is methyl, R² and R³ are methyl,R⁴ is a C₂ alkylene bridge and R⁵ and R⁶ are methyl.
 26. The metalcontaining complex of claim 23 wherein M is Hf, R¹ is methyl, R² and R³are methyl, R⁴ is a C₂ alkylene bridge and R⁵ and R⁶ are methyl.
 27. Themetal containing complex of claim 23 wherein M is Zr, R¹ is methyl, R²and R³ are methyl, R⁴ is a C₂ alkylene bridge and R⁵ and R⁶ are methyl.28. The metal containing complex of claim 23 wherein M is Ti, R¹ ist-butyl, R² and R³ are methyl, R⁴ is a C₂ alkylene bridge and R⁵ and R⁶are methyl.
 29. The metal containing complex of claim 23 wherein M isHf, R¹ is t-butyl, R² and R³ are methyl, R⁴ is a C₂ alkylene bridge andR⁵ and R⁶ are methyl.
 30. The metal containing complex of claim 23wherein M is Zr, R¹ is t-butyl, R² and R³ are methyl, R⁴ is a C₂alkylene bridge and R⁵ and R⁶ are methyl.
 31. The metal-containingcomplex of claim 1 represented by structure C wherein M is selected fromthe group consisting of Ca, Sr, and Ba.
 32. The metal containing complexof claim 31 wherein R¹ is selected from the group consisting of t-butyland t-pentyl, R² and R³ are methyl, R⁴ and R⁵ each are a C₂ alkylenebridge, R⁶ and R⁷ are individually selected from the group consisting ofmethyl and ethyl, and X is selected from the group consisting of oxygenand NCH₃.
 33. The metal containing complex of claim 31 wherein M is Ba,R¹ is t-butyl, R² and R³ are methyl, R⁴ and R⁵ each are a C₂ alkylenebridge, R⁶ and R⁷ are methyl, and X═NCH₃.
 34. The metal containingcomplex of claim 1 dissolved in a solvent selected from the groupconsisting of glyme solvents having from 1 to 20 ethoxy —(C₂H₄O)— repeatunits; C₂-C₁₂ alkanols, organic ethers selected from the groupconsisting of dialkyl ethers comprising C₁-C₆ alkyl moieties, C₄-C₈cyclic ethers; C₁₂-C₆₀ crown O₄-O₂₀ ethers wherein the prefixed C_(i)range is the number i of carbon atoms in the ether compound and thesuffixed O_(i) range is the number i of oxygen atoms in the ethercompound; C₆-C₁₂ aliphatic hydrocarbons; C₆-C₁₈ aromatic hydrocarbons;organic esters; organic amines; and polyamines and organic amides. 35.The precursor source of claim 34 wherein the solvent is an organic amideselected from the group consisting N-methyl-2-pyrrolidinone,N-ethyl-2-pyrrolidinone, and N-cyclohexyl-2-pyrrolidinone.
 36. A vapordeposition process for forming a conformal metal oxide thin film on asubstrate wherein a precursor source and an oxygen containing agent areintroduced to a deposition chamber and a metal oxide film deposited on asubstrate, the improvement which comprises using the metal containingcomplex of claim 1 as said precursor source.
 37. The process of claim 36wherein the vapor deposition process is selected from the groupconsisting of chemical vapor deposition and atomic layer deposition. 38.The process of claim 36 wherein the oxygen containing agent is selectedfrom the group consisting of water, O₂, H₂O₂, ozone and mixturesthereof.
 39. A vapor deposition process for forming a conformal metalthin film on a substrate wherein a precursor source and a reducing agentare introduced to a deposition chamber and a metal film deposited on asubstrate, the improvement which comprises using the metal containingcomplex of claim 1 as said precursor source.
 40. The process of claim 39wherein the reducing agent is selected from the group consisting ofhydrogen, hydrazine, monoalkylhydrazine, dialkylhydrazine, ammonia, andmixtures thereof.
 41. A vapor deposition process for forming a conformalmetal oxide thin film on a substrate wherein a solution of precursorsource and an oxygen containing agent are introduced to a depositionchamber and a metal oxide film deposited on a substrate, the improvementwhich comprises using a solution of comprised of the metal containingcomplex of claim 1 dissolved in a solvent selected from the groupconsisting of glyme solvents having from 1 to 20 ethoxy —(C₂H₄O)— repeatunits; C₂-C₁₂ alkanols, organic ethers selected from the groupconsisting of dialkyl ethers comprising C₁-C₆ alkyl moieties, C₄-C₈cyclic ethers; C₁₂-C₆₀ crown O₄-O₂₀ ethers wherein the prefixed C_(i)range is the number i of carbon atoms in the ether compound and thesuffixed O_(i) range is the number i of oxygen atoms in the ethercompound; C₆-C₁₂ aliphatic hydrocarbons; C₆-C₁₈ aromatic hydrocarbons;organic esters; organic amines; and polyamines and organic amides.
 42. Avapor deposition process for forming a conformal metal thin film on asubstrate wherein a solution of a precursor source and a reducing agentare introduced to a deposition chamber and a metal film deposited on asubstrate, the improvement which comprises using a solution comprised ofthe metal containing complex of claim 1 dissolved in a solvent selectedfrom the group consisting of glyme solvents having from 1 to 20 ethoxy—(C₂H₄O)— repeat units; C₂-C₁₂ alkanols, organic ethers selected fromthe group consisting of dialkyl ethers comprising C₁-C₆ alkyl moieties,C₄-C₈ cyclic ethers; C₁₂-C₆₀ crown O₄-O₂₀ ethers wherein the prefixedC_(i) range is the number i of carbon atoms in the ether compound andthe suffixed O_(i) range is the number i of oxygen atoms in the ethercompound; C₆-C₁₂ aliphatic hydrocarbons; C₆-C₁₈ aromatic hydrocarbons;organic esters; organic amines; and polyamines and organic amides.